Sodium thiosulfate (Na2S2O3), also spelled sodium thiosulphate, is an inorganic compound that is typically available as the pentahydrate, Na2S2O3·5H2O. The solid is an efflorescent (loses water readily) crystalline substance that dissolves well in water. It is also called sodium hyposulfite or “hypo”.[2]

It is used as an antidote to cyanide poisoning.[7][8] Thiosulfate serves as a sulfur donor for the conversion of cyanide to thiocyanate (which can then be safely excreted in the urine), catalyzed by the enzyme rhodanase.

It is used in the management of extravasations during chemotherapy. Sodium thiosulfate prevents alkylation and tissue destruction by providing a substrate for the alkylating agents that have invaded the subcutaneous tissues. The dose may be 2 ml of 0.17 M (a solution of 4 ml 10% sodium thiosulfate and 6 ml sterile water for injection). It may be instilled subcutaneously into multiple sites using a small-gauge needle. Data are limited on this method with few recommendations.[citation needed]

Due to the quantitative nature of this reaction, as well as because Na2S2O3·5H2O has an excellent shelf-life, it is used as a titrant in iodometry. Na2S2O3·5H2O is also a component of iodine clock experiments.

This particular use can be set up to measure the oxygen content of water through a long series of reactions in the Winkler test for dissolved oxygen. It is also used in estimating volumetrically the concentrations of certain compounds in solution (hydrogen peroxide, for instance) and in estimating the chlorine content in commercial bleaching powder and water.

Sodium thiosulfate is a component of an alternative lixiviant to cyanide for extraction of gold.[11] However, it forms a strong soluble complex with gold(I) ions, [Au(S2O3)2]3−. The advantage of this approach is that thiosulfate is essentially not toxic and that ore types that are refractory to gold cyanidation (e.g. carbonaceous or Carlin-type ores) can be leached by thiosulfate. Some problems with this alternative process include the high consumption of thiosulfate, and the lack of a suitable recovery technique, since [Au(S2O3)2]3− does not adsorb to activated carbon, which is the standard technique used in gold cyanidation to separate the gold complex from the ore slurry.

It is used to dechlorinate tap water including lowering chlorine levels for use in aquaria and swimming pools and spas (e.g., following superchlorination) and within water treatment plants to treat settled backwash water prior to release into rivers.[2] The reduction reaction is analogous to the iodine reduction reaction.

In pH testing of bleach substances, sodium thiosulfate neutralizes the color-removing effects of bleach and allows one to test the pH of bleach solutions with liquid indicators. The relevant reaction is akin to the iodine reaction: thiosulfate reduces the hypochlorite (active ingredient in bleach) and in so doing becomes oxidized to sulfate. The complete reaction is:

4 NaClO + Na2S2O3 + 2 NaOH → 4 NaCl + 2 Na2SO4 + H2O

Similarly, sodium thiosulfate reacts with bromine, removing the free bromine from solution. Solutions of sodium thiosulfate are commonly used as a precaution in chemistry laboratories when working with bromine and for the safe disposal of bromine, iodine, or other strong oxidizers.

To demonstrate the concept of supercooling in physics classes: Sodium thiosulfate, when heated, dissolves in its own water of crystallisation. This solution can be cooled to room temperature without recrystallisation. When crystallisation is induced by the addition of a small seed crystal, the sudden temperature rise can be experienced by touch.

Two polymorphs are known of the pentahydrate. The anhydrous salt exists in several polymorphs.[2] In the solid state, the thiosulfateanion is tetrahedral in shape and is notionally derived by replacing one of the oxygen atoms by a sulfur atom in a sulfate anion. The S-S distance indicates a single bond, implying that the terminal sulfur bears significant negative charge and the S-O interactions have more double-bond character.

Upon heating to 300 °C, it decomposes to sodium sulfate and sodium polysulfide:

4 Na2S2O3 → 3 Na2SO4 + Na2S5

Thiosulfate salts characteristically decompose upon treatment with acids. Initial protonation occurs at sulfur. When the protonation is conducted in diethyl ether at −78 °C, H2S2O3 (thiosulfuric acid) can be obtained. It is a somewhat strong acid with pKas of 0.6 and 1.7 for the first and second dissociations, respectively.

Under normal conditions, acidification of solutions of this salt excess with even dilute acids results in complete decomposition to sulfur, sulfur dioxide, and water:[14]

Na2S2O3 + 2 HCl → 2 NaCl + S + SO2 + H2O

This reaction is known as a "clock reaction", because when the sulfur reaches a certain concentration, the solution turns from colourless to a pale yellow. This reaction has been employed to generate colloidal sulfur. This process is used to demonstrate the concept of reaction rate in chemistry classes.